Fuel oil composition



Patented 31,1950

' FUEL OIL COMPOSITION.

John B. R. Caron, North Plainfield, N. J., Calm Wiea, New York, N. Y., and Everett B. Glendenning, Cranford, N. J., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application March 29, 1948,

Serial No. 17,804

20 Claims.

This invention pertains to hydrocarbon fuels. and more particularly to fuel oil compositions capable of preventing or inhibiting the sludging and/or clogging tendencies generally exhibited by hydrocarbon fuels, such as those utilized in burner systems, diesel and combustion engines, and various other industrial and domestic equipment. In addition, this invention relates to fuel oil compositions capable of removing preformed deleterious matter from filters, screens, and the like, caused by deterioration and/or the presence of foreign bodies (e. g. water) in the fuel oils.

Hydrocarbons, such as distillate fuels, for example, those having a normal distillation range of fromabout 300 F. to about 700 F. and particularly from about 340 F. to about 640 F., generally have a marked tendency to deteriorate under oxidizing conditions, and to form sludge. Also, the presence of impurities in such fuels, such as the presence of moisture, dispersed water, organic and/or inorganic foreign matter, and the like, causes the formation of insoluble products, which tend to settle out and adhere to surfaces with which they come in contact, thereby in turn, causing clogging or plugging of filters, strainers, screens, conduit lines, and the like, of the equipment in which they are used. This necessitates frequent cleaning and even replacement of parts, thereby markedly decreasing the performance efflciency of various equipment which utilizes such fuel oils.

The problem of screen clogging is common, particularly in domestic fuel oil systems employ; ing distillate fuel oils produced by distilling or cracking of petroleum which fuels are characterized by their relatively low viscosity and other properties. Fuel oils of this type generally conform to the specifications set forth in Commercial Standards C. S. 12-40 for Nos. 1, 2 and 3, fuel oils. Petroleum distillates within the ranges specified and which generally do not exceed 700 F. and preferably are below 675 F. for use as diesel fuels for further examples of the type of oils which under conditions described have a tendency toward screen or filter clogging, particularly when they contain minor amounts of water dispersed therein.

Another place where screen clogging and plugging of conduit lines is encounteredis in storage tanks for fuel oils, which tanks may be connected to the burner systems or engines, etc. The

stored fuel generally comes in contact with air.

moisture, water, etc., which cause formation and precipitation of sludge material which, in turn, deposit on and clog the screens or filters used 2 for protecting the burners or engines which use such oils as the fuel.

It is an object of this invention to inhibit sludging tendencies of hydrocarbon fuel oils. It is another object of this invention to inhibit sludging and precipitation of contaminants in hydrocarbon distillate fuel oils, and particularly in cracked hydrocarbon fuels. It is still another object of this invention to provide distillate fuel oils, particularly-fuel oils obtained by cracking of hydrocarbons, which fuels have excellent performance characteristics with respect to freedom from screen clogging, even after extensive storage under oxidizing conditions and in the presence of water. Still another object of this invention is to provide a distillate fuel oil composition which is effective in removing preformed sludge deposits formed in fuel oil systems. Still another object of this invention is to provide distillate fuel oil compositions, and blends thereof, which are non-corrosive and stable, and which are effective for cleaning and for sludge removing.

minor amount ofa detergent and/or a solutizer may also be added to the composition.

The hydrocarbon distillate fueloils in which the active ingredient and/or ingredients of this invention are dispersed or dissolved may be treated -or untreated catalytically cracked fuel oils, or mixtures of cracked fuels with straightrun fuel oils, which have an initial distillation point of about 300 F. and an end distillation point not exceeding '100' F. Generally, these fuels have a boiling range of from about 340 F.

to about 700 F., and preferably a boiling range of from about 400 F. to about 675 F.

Cracked fuels may be obtained by thermal or I catalytic cracking of certain petroleum hydrocarbon feed stocks. Both types of cracked fuels, as well as blends of cracked and straight-run fuels, may be acid and/or caustic-treated to improve their stability. Specifically, hydrocarbon distillates which are utilized as bases in compositions of this invention are cracked gas oils, fuel oils, furnace oils, burner oils, diesel fuel oils, kerosene, etc., and mixtures of said cracked fuels 3 with the corresponding or like straight-run hydrocarbon fractions, e. g., fuel oils, etc.

The properties of a caustic-treated catalytically cracked light gas oil, and of a 50-50 blend of an untreated catalytically cracked light gas oil and of a straight-run acid-treated gas oil, both 01 which have marked tendencies toward clogging screens, etc., are given in the following table:

5040 Blend of Cote lytically Cracked Cnralyhmlly Properties Light Gas Oil and Cracked Gas Strai lit-Run Light Oil Gas il Gravity, A lI 32. 6 31.0 ASTM liisi, ii:

1BR-.. 414 434 EBP 004 020 Sulfur, Per (rm- W, 0. 830 0. 783 Conradscn (Lirlmn Residue {HY}; Buns) Per Cent M..-

0.01 0.01 Four Point, H1

The surface active agents which possess the unique property of inhibiting sludge formation or of removing preformed deposits fromsurfaces (thereby preventing clogging of systems utilizing fuels normally susceptible of causing such deterioration) are the alkali metal salts of petroleum sulfonic acids, which acids are preferably of high molecular weight and are derived from petroleum hydrocarbon crudes and fractions thereof which normally possess lubricating properties, which hydrocarbons are of the so-called mixed type, i. e. containing naphthenic type hydrocarbons. Specifically, the preferred petroleum sulfonic acids used to form the alkali metal salts are derived from naphthenic, Gulf Coastal or Mid-Continent oils.

A naphthenic oil which is particularlypreferred for the production of said acids may be a distilled naphthenic oil having the following properties:

Viscosity SSU at 100 F 400 to 900, and preferably 550 Viscosity index 50 to 60 Pour point, F 10 to Iodine No. (Hanus) l0 Unsulfonatable residue 80 min.

A Mid-Continent oil which may be used may have the following properties:

Gravity, API 26.0 to 29.5 Pour point, F to 10 Flash (C. O. C.), F 410-445 Fire, F 500 Viscosity SSU at 100 F 400-540 Cracked and recycle stock of the gasoline or kerosene boiling range, as well as Pennsylvania or parafilnic oils, are generally unsuitable as starting materials for the manufacture of sulfonates of this invention.

According to the present invention, a naphthenic or Mid-Continent oil having a viscosity SSU (at 100 F.) in the range of from 400 to 900, may be sulfonated with sulfuric acid, oleum, chlorosulfonic acid, sulfur trioxide or their mixtures. After the oil has been sulfonated, the

sludge formed is removed and the acid-treated oil containing the dissolved oil-soluble sulfonic acids may be neutralized with a solution of sodium hydroxide, or any other base of a suitable'alkali metal, such as potassium, lithium, rubidium, or cesium, or mixtures thereof. The aqueous alkali solution thus formed is removed from the mixture, and the alkali metal salt of petroleum sulfonic i acid extracted with alcohol. The alcohol layer containing the sulfonate may be subjected to distillation or any other suitable treatment to remove the alcohol. and thus leave the sulfonate.

The sulfonated oil thus formed should have a molecular weight of from about 475 to about 650,- and preferably from about 480 to about 570, and contain a plurality of cycloalkyl groups in the molecule.

In cases where the sulfonate is obtained from a naphthenic oil, the produce need not be subjected to a high degree of purification. However, if Mid-Continent oils, or blends of Mid-Continent and naphthenic oils, are used, it is preferable that the resultant oil-soluble sulfonated product be subjected to purification. This purification (which removes inorganic salts and other undesirable ccntaminants) may be carried out as follows: The crude sulfonate may be admixed with approximately an equal volume of a light hydrocarbon, such as a highly paraifinic hydrocarbon having a boiling range of from about F. to about 260 F., and hydrocarbon layer removed by settling, decantation or the like, to produce the purified sulfonates as a distillation residue. Alternately, the highly paraflinic hydrocarbon may be added prior to neutralization of the alcohol-sulfonic acid mixture, and the entire mixture neutralized. The parafilnic hydrocarbon is then removed in the manner described above or by any other suitable means.

Analysis of the impurities present in sulfonates before and after purification is given below:

Thus, petroleum sulfonates produced from 400 SSU at 100 F. Mid-Continent oil may be purified in the following manner: The purification of the sulfonates can be carried out by extracting the sulfonates from the acid alcoholic sludge with a low boiling highly parafilnic hydrocarbon and neutralizing the mixture with 30 B. caustic. The neutralization separates the mixture into two layers. The bottom layer containing the caustic sludge layer is drawn off. The top layer is drawn off. The top layer is distilled to remove the light hydrocarbon and the purified sulfonates remain as heavy bottoms. Analysis of the purified product was as follows:

Per cent Sodium petroleum sulfonate obtained from a 400 SSU at 100 F. (Mid-Continent raflinate) 53.6 Oil, 46.0 Free alkali 0.0

Sodium sulfate 0.0 Water and alcohol 0.4

Oil-soluble alkali metal petroleum sulfonates from naphthenic, Gulf Coast and/or Mid-Continent Stocks, may be also obtained by other processes. such as those disclosed in the U. S. Patents, Nos. 2,388,677, 2,395,713, 2,413,199, 2.- 41.3,311, 2,414,773, 2,416,397, and, if desired purified by such means as those disclosed in U. S. Patents, Nos. 2236,9133, 2,334,532, 2,357,866, 2,- 368,452, and 2,406,753.

The amount of alkali metal salt of the petroleum sulfonic acid derived from a non-parafflnic petroleum stock defined above, which salt answer 8 is to be present in the base or concentrate fuel oil, may vary from about 2%, and 25%, and pref.- erably between about 5% and 20%, by weight. However, greater or lesser concentrations may also be used.

If desired, and under certain conditions ofuse. it is preferred to add detergents to compositions of this invention. The function of the detergent agents in compositions of this invention is to act as peptizers, to aid in inhibiting or preventing the settling and adhering of impurities and of sludge to surfaces, and to allow .any impurities present or' formed to pass through the screen or filter system.

Detergents which may be used are alkali, alkaline earth and heavy metal and organic nitrogen base salts of various organic acids. The acidic wherein M is a metal: R and R represent at least one alkyl radical attached to the aromatic ring Ar, the total number of carbon atoms in all of such radicals being at least 5; X is O, 8, Se and/or Te; Q is S, Se or Te; and n is an integer of from 1 to 4.-

These salts may be formed by treating the phenolic compounds with such metal compounds as Li, Na, K. Cu, Hg, Fe, Mn, Mg, Ca, Ba, Sr, Pb, Ni, Co, Cr, Sn, Mo, etc. Alkaline earth metals are particularly-preferred because of their solubility inhydrocarbons and their excellent detergent properties.

In addition to the normal salts of phenolic compounds, basic salts represented by the following formula may be used:

' lfi-XH M-XH x R-lr-Qn-lr-JI wherein the symbols are the same as referred to in the previous formulas. These basic salts may be formed by reacting the aromatic acidic compound with more than the amount of metal oxide or hydroxide necessary to form the normal salt.

5 of detergent salt used In systems wherein substantial amounts of' moisture are present, a drying agent may be added which is compatible with the active ingredients of this invention. By tying up most of the free moisture in this manner, the amount thereof which would normally combine with sludgeforming materials is diminished, thus alleviating a most aggravating clogging problem.

Drying agents which are particularly suited are the glycol-ethers, such as diethylene glycol monomethyl, ethyl, N- and isopropyl ether, di-

ethylene glycol mono-bvtyl ether, diethylene gly- The following are illustrative examples of the col mono-decyl ther, etc.; also dipropylene glycol mono ethyl ether, dipropylene glycol mono-isopropyl ether, dipropylene glycol mono-isoamyl ether, diisobutylene glycol-mono isopropyl ether, ethylene-propylene glycol mono ethyl ether, ethylene-isobutylene glycol mono-isopropyl ether, etc. Instead of the glycol-ethers,.various alcohols may be used, such as diols having 6 or more carbon atoms in the molecule, e. g. hexylene glycol, decylene glycols, cetylene glycols, etc.; diglycols such as dipropylene glycols, dibutylene glycol, diamylene glycol, ether alcohols and particularly the glycol mono alkyl ethers, e. g.- the cellosolves such as ethylene glycol mono ethyl ether, ethylene glycol mono 'propyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyi ether, ethylene glycol mono-hexyl-butyl ether, propylene glycol mono-isoamyl ether, etc. Also glycerine and the like may be used.

The amount of these materials. when used, constitutes a substantial portion of the base or concentrate, and generally is about 50% or more. However, under certain conditions these materials may be omitted from the base.

The following is a general formula of a base (concentrate) composition of this invention:

General Ban :8 Preferred Alkali metal salt of petroleum sulfonic acid of high molecular weight Detergent e. g. salt of alkyl phenol sulflde Drying agent Fuel oil Specific base compositions may be illustrated V by the follo ing examples: I

Composition .4

oil and straight run acid-treated gas 011---- Composition 5 Sodium petroleum sulfonate derivedjrom a 400 SUS at F. Mid-Continent crude 15 Barium salt of alkyl phenol disulflde 10 Caustic treated catalytically cracked light gas 75 oil and 15%, and preferably Per cent lation point of from about 580 F. to 610 F... 80

The following table further illustrates suitable anti-clogging base compositions of this invention.

Com nentsz urlsce Active Agent Na petroleum suilonate from non-paraillnic petroleum v S K petroleum sullonate from non-parailinic petroleum s Li petroleum sulfonate from non-paraillnic petroleum stock Detergent:

Ba salt of alkyl phenol sulfide. Ca salt of alkyl phenol sulfide. Ca alkyl salicylate- Na alkyl ssiicylate-- Ba alkyl salicylate.. Na petroleum naphthenate-. Ca petroleum naphtbenate.- Ethanoiamine oleate Ethanolarnine stem-ate Drying agent:

' Diethylene glycol monobutyl ether Diethylene glycol monoethyl ether Ethglene glycol monobutyl et er Cetylene glycol"... Dipropylene glycol l All or the above compositions are diluted with a hydrocarbon distillate fuel oil in mounts indicated above.

Compositions of this invention are generally mixed in amounts of 1 pint or less with from about 250 to about 100 gallons of fuel oil. Thus. for example. on a percentagebasis of fuel used, one pint of any one of the compositions described above per 250 gallons of fuel would correspond to approximately'the following concentration of the active ingredients in the final fuel compositions Alkali metal salt of petroleum sulfonic acid derived from a non-parafllnic oil, from about 0,0025% to about 0.01% (and 0.025% when calculated that 1 pint of the concentrate containing 20% sulfonate is used for 100 gallons of fuel oil); detergent (salt of an alkyl phenol sulfide), from zero to about 0.0025% or 0.004296; drying agent (glycol-ether), from zero to about 0.0265%.

Example Ii rate was observed, and the screen was perfectly clean.

To inhibit any corrosive tendencies of fuel compositions of this invention a minute amount of caustic or aromatic nitrogen compound, such as aniline, may also be added. These compounds act as alkaline reserves and render the fuel com- Example Hi Approximately 5 gallons of an undoped caustictreated catalytically cracked light gas oil was treated and tested in the same manner as described in Example I. At the end of the test period a decrease in flow rate of approximately 85% was observed, and the screen was found to be stained and coated with sludge.

Example 11! The undoped fuel oil of Example III was doped with Composition B in the same amount as noted in Example II, and the above described test repeated. At the end of the test period no decrease in flow rate was observed, the so een being found to be perfectly clean.

Example V Example VI The undoped fuel oil of Example V was doped with Composition C in the same amount as noted in Example II, and the test repeated. At the end of the fuel test period no decrease in flow rate was observed, and the screen was clean.

Example VII Two fuel tanks were cleaned with acetone and the entire burner system flushed with kerosene. One tank was charged with about 125 gallons of an undoped fuel oil, while the other tank was charged with 125 gallons of fuel oil doped with a half pint of Composition A. Both the doped and undoped fuels were clouded by passage of positions substantially non-corrosivegto copper,

Example 7 Approximately 5 gallons of an undoped fuel oil as defined in Composition A was first treated by blowing steam therethrough until the fuel oil became clouded. This steam treated oil was then circulated by means of a conventional oil burner pump, for approximately 24 hours through an apparatus containing a 100 mesh screen. The drop in flow, as measured by a rotameter placed in the stream, indicated the extent to which the screen became clogged during this test period. A decrease in flow rate of approximately 69.5% for this undoped fuel oil was observed, and the screen, on examination, was found to be stained and coated with sludge.

for 28 days by circulating the oil through burner systems. The condition of each oil, as well as cracked light gas oil was used in this test. The first test was effected using about gallons of this material, while for the second test a like quantity of this fuel was first doped with Composition B employed in an amount equal 'to 1 pint of said Composition 13 per 1000 gallons of the fuel oil. Both oils were clouded by steaming and aged by maintaining them at 150 F. for a period of 24 hours. Each oil was circulated through screens for 24 hours at a rate of about 25 gallons per hour. The conditions of the screens at the end of these tests were as follows:

Area plugged ggg'gg' in sq. in. plugged Caustic treated catalytimily cracked t 13 85 ligh gaso Seine oil 1000 ons)+1 int of Composition B52 0 To compositions ofthis invention may be added minor amounts of foam inhibitors, such as a silicone liquid, e. g., dimethyl silicone, fluoro organic compounds, fluoro parailins, salts of alkyl alkylene phosphates, and the like. Compositions of this with the function of the fluid in which they are dispersed.

We claim as our invention:

1. An anti-clogging concentrate adapted to be added to a hydrocarbon distillate fuel from the tures of cracked and straight run fuel oils and a minor amount of from about to of an oil-soluble alkali metal salt of oil-soluble p'etroleum sulfonic acid having a molecular weight of 10 invention are non-corrosive and do not interfere group consisting of cracked'and mixtures of cracked and straight run fuel oils and normally susceptible toward clogging, said concentrate comprising 15% by weight of oil-soluble sodium salt of oil-soluble petroleum sulfonic acid having a molecular weight of from about 475 to about 650 and derived from a naphthenic petroleum stock,

10% by weight of a barium salt of alkyl phenol disulfide, and 75% by weight of a -50 blend of towards clogging, said concentrate comprising 15% of oil-soluble sodium salt of oil-soluble petroleum sulfonic acid having a molecular weight of from about 475 to about 650 and derived from a naphthenic petroleum stock, 10% of'a barium salt of alkyl phenol disulfide, and of a caustically treated catalytically cracked light fuel oil.

3. An anti-clogging concentrate adapted to be added to a hydrocarbon fuel from the-group consisting of cracked and mixtures of cracked and straight run fuel oils and normally susceptible towards clogging, said concentrate comprising 15% of oil-soluble sodium salt of oil-soluble petroleum sulfonic acid having a molecular weight of from about 475 to about 650 and derived from Mid-Continent crude distillate fraction having a Saybolt viscosity at F. of from 400-600, 10% of a barium salt of alkyl phenol disulfide and 75% of a caustic treated catalytically cracked.

3 an acidic hydroxy aromatic compound.

5. An anti-clogging concentrate adapted to be added to a hydrocarbon distillate fuel from the from about 415m about 650 and derived-from petroleum stocks consisting of the group of Naphthenic, Gulf Coastal, Mid-Continent crude distill'ate fractions and their mixtures and having a Saybolt Universalviscosity at 100 F: of above 400, and a minor amount of a polyvalent salt of an acidic hydroxy aromatic compound.

6. An anti-clogging concentrate adapted to be added to a liquid hydrocarbon fuel from the group consisting of cracked and mixtures of cracked and straight run fuel oils and containing entrained moisture and which is normally susceptible towards clogging, comprising a, major.

amount of a hydrocarbon fuel from the group consisting of cracked and mixture of cracked and straight run fuel oils containing entrained moisture and a minor amount of from about 10 to 20% of an oil-soluble alkali metal salt of oilsoluble petroleum sulfonic acid having a molecular weight of from about 4'75 to about 650 andv derived from petroleum stocks consisting of the group of Naphthenic, Gulf Coastal, Mid-Continent crude distillate fractions and their mixtures, and having a, Saybolt Universal viscosity at 100 F. of above 400, and a minor amount of a polyvalent salt of an acidic hydroxyarom'atic compound.

7. An anti-clogging concentrate adapted to be added to a hydrocarbon fuel from the group consisting of cracked and mixtures of cracked andstraight run fuel oils and normally susceptibletowards clogging; said concentrate comprising a major amount of a hydrocarbon fuel oil containing a substantial amount of cracked hydrocarbon fractions, and a minor amount of from about 10 to 20% of an oil-soluble alkali metal salt of oil-soluble petroleum sulfonic acid having a molecular weight of from about 475 to about 650 and derived from petroleum stock consisting of the group of Naphthenic, Gulf Coastal, Mid-Continent crude distillate fractions and their mixabout 4'75 to about 650 and derived from a naphthenic petroleum stock and a polyvalent metalsalt of an acidic hydroxy aromatic compound.

9. An anti-clogging concentrate adapted to be added to a hydrocarbon fuel oil from the group' consisting of cracked and mixtures of cracked and straight run fuel oils normally susceptible" towards clogging, said concentrate consisting es-' sentially of a major amount of a hydrocarbon distillate fuel oil and a minor amount sufficient to inhibitciogging of an oil-soluble sodium salt of oil-soluble petroleum sulfonic acid having a molecular weight of from about 4'75 to about 650 and derived from a naphthenic petroleum stock.

10. An anti-clogging concentrate adapted to be added to a hydrocarbon fuel oil from the group consisting of cracked and mixtures of cracked and straight run fuel oils normally susceptible towards clogging, said concentrate consisting essentially of a major amount of a hydrocarbon distillate fuel oil and a minor amount sufficient to inhibit clogging of an oil-soluble alkali metal salt of oil-soluble petroleum sulfonic acid having a. molecular weight of from about 475 to about 650 and derived from a naphthenic petroleum stock.

11. A non-clogging fuel oil from the group consisting of cracked and mixtures of cracked and straight run fuel oils and normally susceptible to cause clogging containing in combination therewith from about 0.0025% to about 0.01% of oil-soluble sodium salt of oil-soluble petroleum sulfonic acid having a molecular weight of from about 475 to about 650 and derived from a naphthenic petroleum stock and from about 0.0025% to about 0.0042% of a barium salt of alkyl phenol disulflde.

12. A non-clogging fuel oil from the group consisting of cracked and mixtures of cracked and straight run fuel oils and normally susceptible to cause clogging containing in combination therewith from about 0.0025% to about 0.01% of oil-soluble alkali metal salt of oil-soluble petroleum sulfonic acid having a molecular weight of from about 475 to about 650 and derived from a naphthenic petroleum stock and from about 0.0025% to about 0.0042% of a salt of alkyl phenol disulflde.

13. A non-clogging fuel oil from the group consisting of cracked and mixtures of cracked and straight run fuel oils and normally susceptible to cause clogging consisting essentially of said fuel oil and in combination therewith from @bout 0.0025% to about 0.01% of oil-soluble sodium salt of oil-soluble petroleum sulfonic acid having a molecular weight of from about 475 to about 650 and derived from a naphthenic petroleum stock.

14. A non-clogging fuel oil from the group consisting of cracked and mixtures of cracked and straight run fuel oils and normally susceptible to cause clogging consisting essentially of said fuel oil and in combination therewith from about 0.0025% to about 0.01% of oil-soluble alkali metal salt of oil-soluble petroleum sulfonic acid derived from a naphthenic petroleum stock.

15. A non-clogging fuel oil composition comprising a normally liquid hydrocarbon fuel oil containing substantial cracked components and minute amounts of entrained moisture, said fuel being normally susceptible to cause clogging, and in combination therewith from about 0.0025% to about 0.01 of oil-soluble sodium salt of oil-soluble petroleum sulfonic acid having a molecular weight of from about 475 to about 650 and derived from petroleum stocks consisting of the group of Naphthenic, Gulf Coastal, Mid-Continent distillate fractions and their mixtures and having a Saybolt Universal viscosity at 100 F. of above 400 and from about 0.0025% to about 0.0042% of a barium salt of alkyl phenol disulfide.

16. A non-010881 8 fuel oil composition comprising a normally liquid hydrocarbon fuel oil containing substantial cracked components and minute amounts of entrained moisture, said fuel being normally susceptible to cause clogging, and in combination therewith from about 0.0025% to about 0.01% of oil-soluble sodium salt of oilsoluble petroleum sulfonic acid having a molecular weight of from about 475 to about 650 and derived from petroleum stocks consisting of the group of Naphthenic, Gulf Coastal, Mid-Continent distillate fractions and their mixtures and having a Saybolt Universal viscosity at F. of above 400.

17. A non-clogging fuel 011 comprising a normally liquid hydrocarbon fuel oil containing substantial cracked components and being normally susceptible to cause clogging in the presence of minute amounts of entrained moisture and in combination therewith from about 0.0025% to about 0.025% of oil-soiubie alkali metal salt of oil-soluble petroleum sulfonic acid derived from a naphthenic petroleum stock.

18. A non-clogging fuel oil comprising a normally liquid hydrocarbon fuel oil containing substantial cracked components and being normally susceptible to cause clogging in the presence of minute amounts of entrained moisture and in combination therewith from about 0.0025% to about 0.0042% of a polyvalent metal salt of an acidic hydroxy aromatic compound.

19. An anti-clogging concentrate adapted to be added to a normally liquid hydrocarbon fuel oil containing substantial cracked components and being normally susceptible to cause clogging in the presence of minute amounts of entrained moisture, said concentrate consisting essentially of a major amount of a liquid hydrocarbon distiliate having a boiling range within the range of from 300 to 700 F. and a minor amount sufflcient to inhibit clogging of an oil-soluble alkali metal salt of oil-soluble petroleum sulfonic acid derived from a naphthenic stock.

20. An anti-clogging concentrate adapted to be added to a normally liquid hydrocarbon fuel oil containing substantial cracked components and being normally susceptible to cause clogging in the presence of minute amounts of entrained moisture, said concentrate consisting essentially of a major amount of a liquid hydrocarbon distillate having a boiling range within the range of from 300 to 700 F. and a minor amount sufficient to inhibit clogging of an nil-soluble alkali metal salt of oil-soluble petroleum sulfonic acid derived from a naphthenic stock and a polyvalent metal salt of an acidic hydroxy aromatic compound.

JOHN B. R. CARON.

CAIMY WIES.

EVERE'I'I B. GLENDENNING.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number i Name Date 2,125,305 Murphy Aug. 2, 1938 2,294,145 Winning Aug. 25, 1942 2,336,074 Cook Dec. 7, 1943 2,361,804 Wilson Oct. 31, 1944 2,362,292 McNab Nov. '7, 1944 2,454,825 Faust Nov. 30, 1948 2,454,828 Faust Nov. 30, 1948 @ertificate of Correction .etent No. 2,527,987 Octoher 31 1950 JOHN B. R. GABON ET AL.

It is hereby certified that error appears in the printed specificetion of the above numbered patent requiring correction as follows:

Column 12, line 26, after the word therewith insert from about 0.00%5% to about 0.01% of oil-soluble alkali metal salt of oil-soluble petroleum sulfonic acid deri/ved from a mphthem'e petroleum stool: and

and that the said Letters Patent should be read; as corrected above, so that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 20th day of February, A. D. 1951.

THOMAS F. MURPHY,

Assistant Uommzgsioner of PM. I 

1. AN ANTI-CLOGGING CONCENTRATE ADAPTED TO BE ADDED TO A HYDROCARBON DISTILLATE FUEL FROM THE GROUP CONSISTING OF CRACKED AND MIXTURES OF CRACKED AND STRAIGHT RUN FUEL OILS AND NORMALLY SUSCEPTIBLE TOWARD CLOGGING, SAID CONCENTRATE COMPRISING 15% BY WEIGHT OF OIL-SOLUBLE SODIUM SALT OF OIL-SOLUBLE PERTROLEUM SULFONIC ACID HAVING A MOLECULAR WEIGHT OF FROM ABOUT 475 TO ABOUT 650 AND DERIVED FROM A NAPHTHENIC PETROLEUM STOCK, 10% BY WEIGHT OF A BRIUM SALT OF ALKYL PHENOL DISULFIDE, AND 75% BY WEIGHT OF A 50-50 BLEND OF CATALYTICALLY CRACKED LIGHT GAS OIL AND OF A STRAIGHT RUN ACID TREATED GAS OIL. 